Production of gasproof compound fabrics



Patented Mar. as, 1 48 um'rsos'ra'rss' Parsm orncs 5.438.176 I Louis Amdc mm and Arthur scion em, muicheater, England, assignors to The Calico Printera Association Limited, Manchester, England,

a British company No Drawing. Original application July 16'. 1943, Serial No. 495,077. Divided and this application July s, 1944, Serial No. 544,144. In Great Britain May 20, 1942 Section 1, Public Law 690, August 8, 1946 I Patent expires May 20, 19,62

11 Claims. (Cl. 154-140) This application is a division of our prior application, Serial Number 495,077, filed July 16, 1943, now abandoned.

The invention relates to the production of fabrics which are impervious to war gases, both in the vapour and liquid form, and p la ly to the vesicant type of gas, such as mustard gas.

Our invention comprises a process for producing a gas-proof compound material by combining two or more webs by means of an interlayer or interlayers consisting of a polyvinyl alcohol or water-soluble partial polyvinyl alcohol applied in aqueous solution to one or moreof said webs in presence of an acid catalyst and so much of an aldehyde as is suflicient only to insolubilise the amount of polyvinyl alcohol present.

Our invention further comprises the production of a gas-proof compound fabric by coating one side of one of the webs constituting the compound fabric with an aqueous solution of a polyvinyl alcohol or water soluble partial polyvinyl alcohol containing an acid catalyst and so much of an aldehyde as is sufllcient only to insolubilise the amount of polyvinyl alcohol present (with which it acts preferentially) so that any cellulosic material present in the fabric is not reacted with the formaldehyde, drying the coated web, applying a further portion of the coating to the coated web, superimposing the webs with the uncoated face of one web against the damp coated face of ,the other web, joining the webs firmly by pressure, and finally heating the compound fabric to dry it and to form in situ a condensation product of polyvinyl alcohol which is insoluble both in water and organic solvents.

Our invention further comprises coating two webs as aforesaid, drying the coated webs, applying a further coating to one of the webs, superimposing the two webs whilst the further coated web is still wet so that the coated sides of the two webs come together, joining the two webs firmly by pressure, and finally heating the compound iabric to dry it and insolubilise the polyvinyl alcohol. I

Our invention further comprises coating two websas aforesaid, drying the webs, damping the coated side of at least one web, superimposing the two webs sotliat the coated sides come together, pressing the webs firmly together, and finally heating the compound fabric to dry it and insolubilise the polyvinyl alcohol.

Our invention further comprises coating a web on both sides with a coating as aforesaid, then whilst the coatings are damp or wetted applying uncoated webs to the opposite sides of the coated heating the compound fabricto dry it and in-' solubilise the polyvinyl alcohol.

The product resulting from the reaction of water-soluble partial polyvinyl alcohols with an aldehyde on the fibre has the advantage of decreased swellability in water compared with the corresponding products obtained from pure or practically pure p l vinyl alcohol. The words polyvinyl alcohol as used in this specification are, for the sake of brevity, meant to include such water-soluble partial polyvinyl alcohols. Exam ples of water soluble partial polyvinyl alcohols are polyvinyl ester-alcohols, polyvinyl acetal-alcohols and polyvinyl ester-acetal-alcohols. I I When using formaldehyde we find that a proportion of aldehyde to polyvinyl alcohol. up to 40% gives the desired results and whilst a larger proportion may be used, the liability to reaction with cellulosic material increases. The proportion of formaldehyde may, however, be as low as 2.5%, based on the polyvinyl alcohol, under suitable conditions of heating and with an appropriate catalyst. V

Instead of formaldehyde, we may use as equivalents its homologues such as acetaldehyde, propaldehyde, butaldehyde, or polymers thereof, such as paraformaldehyde, para-aldehyde, meta-aldehyde: or substitution products, such as chloral,

chloral hydrate, and aldol; or unsaturated aliphatic aldehydes such as acrolein, crotonaldehyde and citral; or dialdehydes, such as glyoxal; or aromatic aldehydes, such as benzaldehyde and alkyl-, halogen-, nitro-, hydroxy-, and alkoxysubstituted benzaldehydes; aldehydes in which the functional group is attached to the side chain of an aromatic nucleus, such as cinnamic aldehyde; or'heterocyclic aldehydes, such as furfural. Practically any acid may be used as the catalyst, but acids of medium strength, such as lactic, citric, tartaric, oxalic, formic and chloracetlc acids and the aromatic'sulphonic acids appear to be the most suitable. Weak volatile acids like acetic acid have little catalytic action, and strong mineral acids, such as hydrochloric and sulphuric acids may only be used with great precautions, for fear of attacking the fibrous material.

Instead of free acids, substances which develop acid on heating may be used. such as ammonium salts or hexamethylene' tetramine salts,'or salts of other aliphatic or aromatic amines. in which results.

ing the compoundinaterial to insolub'iiise the polyvinyl alcohol.

Two coated and dried webs may also be combined without an additional adhesive coating, by damping the coated sides of the two webs, pressing them together, and drying and heating the compound material.

In another manner of producing a compound material, a web is coated on both sides with the aldehyde, nature and proportion, of the acid catalyst, time and temperature of heating. These factors are to a large extent interdependent, and equally satisfactory results may be obtained with different sets of conditions; for instance, we may use the same aldehyde and acid catalyst, and.

either heat for a long time at a comparatively low temperature, or for a short time at a com- I paratively high temperature; or we may keep the temperature constant and vary the acid catalyst, so as to modify the time of heating. It is therefore possible to adjust the process so as to adapt it to the plant available. Temperatures ranging from about 60 to about 200 C. have been found satisfactory in practice. When using temperatures in the region of 180-200" C., impregnating liquors of an acidity as low as pH 6.0 may be used. I

In the coating of webs or fabrics we may use any of the devices commonly used for the purpose, in which the coating paste is either poured on the web or fabric and the excess scraped oif by a blade or similar device, or applied to the web or fabric in controlled quantity by means of an engraved roller or the like. The web or fabric may be prepared prior to coating with a sizing agent which controls the penetration of the coatmg mixture into the web or fabric, such as starches, gums, proteins, resins, both natural and synthetic, and water-repelling agents. These substances may be left in the web or fabric or washed out after insolubilisation of the polyvinyl alcohol coating. -The coated material may be dried on heated metal cylinders, either with the coated side upwards oragainst the metal, or it may be dried in hot air by known methods. More than one coating may be given either on the same side or on both sides of the web or fabric.

The heating which follows the drying of the coated material may be carried out on heated cylinders or in a hot-air machine, either by prolonging the drying operation for the time necessary to complete the reaction between polyvinyl alcohol and aldehyde, or it may be carried out as a separate operation. 1

After heating, the coated web or fabric may be washed to remove soluble substances. The coatingis insoluble both in water and organic solvents.

It is necessary to apply to the web or fabric a sufliciency. of coating paste in one or preferably two ormore coating operations to form after drying and insolubilising a continuous layer on and/or partly in the material. V

- Compound materials having a gas-proof interlayer may be produced by coating one or both of the webs which are to be assembled with a solution of a polyvinyl alcohol or water-soluble partial polyvinyl alcohol containing an aldehyde and an acid catalyst, drying the coated web or webs, ap-- plying a further coating to one of the webs, superpolyvinyl alcohol solution and then combined in the damp state by pressure and heat with an uncoated web on each side.

Example 1.-Two webs of heavy cotton canvas are coated each on one side with an aqueous solution containing 20% polyvinyl alcohol, 5% glycerol, 5% aldol, and 2% hexamethylene tetramine lactate. Each fabric is then dried, coated side ,downwards, on a steam-heated metal cylinder having a polished surface, and subsequently heated for four minutes at 140 C. The result is a flexible, highly glazed coating which is resistant to abrasion and to water. The two coated webs are now damped andgsuperimposed with their coated sides facing each other. The assembled material is then subjected to heat (about 100 C.) and pressure in a blanket calender, resulting in the fusion of the two coating layers and the production of a leather-like, extremely resistant, laminated sheet.

Example 2.An aqueous solution is prepared containing 10% of 40% formaldehyde solution, 5% glycerol, 1% oxalic acid, and 30% of a poly vinyl ester-acetal-alcohol in which of the total hydroxyl groups are free, 30% are substituted by ethylidene radicals, and 15% by acetyl radicals.

Each of two pieces of a linen canvasis coated once with the above solution and dried. One

of the pieces is then coated a second time with wax. It isthen coated twice with an aqueous soluimposing the other web without previous drying and in such a manner that the coated sides of the two webs come together, joining the two webs firmly by pressure, and finally drying and heattion of 25% of the polyvinyl-ester-acetal-alcohol described in Example 2, 7.5% polygiycerol, 3% dimethylol urea, of 40% formaldehyde solution,

and 2.5% of hexamethylene tetramine oxalate.

.It is dried after each coating, and then heated at C. for 2 minutes. The cloth is then passed through a weak solution of ammonia to remove residual acid and formaldehyde. The two coated webs are then damped and pressed together in a blanket calender with their coated sides facing each other. The result is a laminated material which has excellent resistance to mustard gas and does not appreciably swell in water.

What we claim is: v

1. A methodof producing a composite flexible fabric adapted to resist penetration of liquid and gaseous chemical warfare agents, comprising applying to a plurality of fabric webs an aqueous solution containing a substance selected from the group consisting of polyvinyl alcohol and watersoluble partial polyvinyl alcohols, an acid catalyst, and an aldehyde in a quantity suflicient only to insolubilise the alcohol, combining the webs by means of the interlayers formed from this solution and then heating to form a condensation product in situ which is insoluble both in water and organic solvents.

- 2. A method of producing a composite flexible abric adapted to resist penetration by liquid and raseous chemical warfare agents, from two fabric vebs, comprising coating one side of one of the vebs with an aqueous solution containing a subtance selected from the group consisting of poly- 'inyl alcohol and water-soluble partial polyvinyl LlCOhOlS, an acid catalyst, and an aldehyde in a uantity sutficient only to insolubilise the alcohol vithout reacting with cellulosic material in the 'abric, drying the coated web, applying a second :oating to the coated side of the web, superimiosing the uncoated web on to the damp coated iide of the other web, applying pressure to join .he Webs firmly together, and heating the composite fabric to dry it and to form in situ a con-" :iensation product of polyvinyl alcohol which is insoluble both in water and organic solvents.

3. A method of producing a composite flexible fabric adapted to resist penetration by liquid and gaseous chemical warfare agents, from two fabric webs, comprising coating one side of each of the webs with an aqueous solution containing a substance selected from the group consisting of polyvinyl alcohol and water-soluble partial polyvinyl alcohols, an acid catalyst, and an aldehyde in a quantity sufflcient only to insolubllise th alcohol without reacting with cellulosic material in the fabric, drying the coated webs, damping the coated side of at least one web, superimposing the webs with their coated sides in contact, applying pressure to join the webs firmly together, and heating the composite fabric to dry it and to form in situ a condensation product of polyvinyl alcohol which is insoluble both in water and organic solvents.

4. A method of producing a composite flexible fabric adapted to resist penetration by liquid and gaseous chemical warfare agents, from a plurality of fabric webs, comprising coating a web on both sides with an aqueous solution containing a substance selected from the group consisting of polyvinyl alcohols and water-soluble partial polyvinyl alcohols. an acid catalyst and an aldehyde in a quantity sufficient only to insolubllise the alcohol without reacting with cellulosic material in the fabric, applying uncoated webs on both sides of the coated web, pressing and finally heating the composite fabric to dry it and to form in situ a condensation product of polyvinyl alcohol which is insoluble both in water and organic solvents.

5. A method of producing a composite flexible fabric adapted to resist penetration by liquid and gaseous chemical warfare agents, from two fabric webs, comprising coating one side of each of thewebs with an aqueous solution containing a substance selected from the group consisting of polythe webs firmly together vinyl alcohol and water-soluble partial polyvinyl alcohols, an acid catalyst, and an aldehyde in a quantity sufficient only to insolubllise the alcohol without reacting with cellulosic material in the fabric, drying one of the coated webs, superimposing the webs with their coated sides in contact whilst one is still damp, applying pressure to join the webs firmly together, and heating the composite fabric to dry it and to form in situ a condensation product of polyvinyl alcohol which is insoluble both in water and organic solvents.

6. A composite flexible fabric adapted to resist penetration by liquid and gaseous chemical warfare agents, especially vesicant liquids such as mustard gas, consisting of a plurality of fabric webs secured together by interlayers of a condensation product, insoluble in both water and organic solvents, of an aldehyde with a substance selected from the group consisting of polyvinyl alcohol and water-soluble partial polyvinyl alcohols in the presence of an acid catalyst, said condensation product being formed and insoluabout 2.5 to 40 per cent by weight equivalents of formaldehyde, based on the weight of the polyvinyl alcohol.

8. The process of claim 1 wherein the aldehyde employed is formaldehyde.

9. The process of claim 1 wherein from about 2.5 to 40 per cent of formaldehyde, based on the weight of the polyvinyl alcohol, is employed as the aldehyde.

10. The process of claim 1 wherein the heating step is conducted at temperatures ranging from about 60 to 200 C.

11. The process of producing a composite flexible fabric adapted to resist penetration of liquid and gaseous chemical warfare agents, which comprises superimposing at least two plies of fabric material with a damp layer therebetween comprising an aqueous solution of a water soluble polyvinyl alcohol, an acid catalyst of medium strength and formaldehyde in amount ranging from about 2.5 to 40 per cent of the weight of the polyvinyl alcohol, pressing and heating the water and organic solvents.

LOUIS AMEDEE LANTZ. ARTHUR SCHOFIELD.

REFERENCES crrEn The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,111,286 Aylsworth Sept. 22, 1914 2,044,730 Kuehn June 16, 1936 2,162,678 Robertson June13, 1939 2,037,049 Sager Apr. 14, 1936 2,173,781 Gibello Sept. 19, 1939 

